Poly(ethylene oxide) (PEO) polymer, in linear and star form, was covalently grafted to silicon surfaces, and the surfaces were tested for their ability to adsorb proteins. Linear PEG of molecular weight 3400, 10 000, and 20 000 g/mol and star PEO molecules were coupled via their terminal hydroxyl groups activated by tresyl chloride to aminosilane-treated silicon wafers. The amount of PEO coupled to the surface was varied by changing the concentration of the tresyl-PEO solution. The dry PEO thickness on the surface was measured using X-ray photoelectron spectroscopy (XPS) and ellipsometry, from which the grafting density was calculated. The PEO surfaces were exposed to solutions of each of three proteins: cytochrome-c, albumin, and fibronectin. The degree of adsorption of each protein was determined by XPS and ellipsometry and recorded as a function of PEO grafting density. All three proteins were found to reach zero adsorption at the highest grafting densities on all three PEG surfaces, which for all three PEG surfaces was a PEO content of 100 +/- 10 ng/cm2. On both star PEO surfaces, albumin and fibronectin decreased to zero adsorption at intermediate values of grafting density, whereas cytochrome-c continued to adsorb at all grafting densities, although with a decreasing trend. A physical model of the surface helped explain these protein adsorption results in terms of the spacing and degree of overlap of grafted PEO chains.
SynopsisTransparent crosslinked PVA hydrogels were prepared by electron beam irradiation of aqueous solutions under nitrogen. These weak hydrogels, upon swelling a t 30 "C in water, showed low elastic moduli (up to 50 psi), low ultimate tensile strength (up to 4 psi), and low extensibility to break (not higher than 85%). Values of the molecular weight between crosslinks M , were calculated from swelling and from tensile experiments. In fact, two values of M , were calculated for each swelling experiment, (a) allowing for observed variation in the polymer-solvent interaction parameter x1 with concentration, and (b) fixing x1 = 0.494 according to literature data. The correlation of the M,. obtained from tensile data with the M , obtained from swelling data, by (a) or (b), was approximately linear and gave the same per cent agreement.
Aqueous poly(vinyl alcohol) solutions were crosslinked via electron‐beam irradiation to form transparent hydrogels of varying crosslinking densities. Typical crosslinked hydrogels with Mc between 3500 and 8000 were weak, easily shattered, nonextensible materials with very low tensile moduli (up to 70 psi) and tensile strengths at break (less than 10 psi). Reinforcement by induction of partial crystallization was accomplished by a two‐stage drying process, consisting of a slow dehydration stage at room temperature and an annealing stage at elevated temperatures, which was mainly responsible for the introduction of the crystallites. The swollen hydrogels after the annealing process had crystallinities widely varying between 30 and 65% and polymer volume fractions between 30 and 60%, depending on the temperature‐time history of the specimen. These materials showed greatly improved mechanical properties (modulus, ultimate tensile strength, tear strength), as compared to the uncrystallized hydrogels.
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